Castable fibrous refractory compositions and articles obtained therefrom



United States Patent 3,253,936 CASTABLE FIBROUS REFRACTORY COMPOSI- TIONS AND ARTICLES ()BTAINED THERE- FROM Herman F. Weindel, Uniondale, N.Y., assiguor to Socony Mobil Oil Company, Inc, a corporation of New York No Drawing. Filed June 10, 1963, Ser. No. 286,526 5 Claims. (Q1. 10664) This invention is directed to castable fibrous refractory compositions which are capable of being cast into improved refractory articles of various shapes using simple casting techniques.

The use of fibrous refractory materials in the production of refractory elements used in various furnaces, reactors, etc. is known. In general, the refractory elements are produced by mixing the fibrous refractory materials with a suitable binder such as a water suspension of a silica material to form a free flowing castable mix which is then cast.

The production of refractory elements from these fibrous refractory materials using simple, conventional casting techniques, does, however, present several problems. First of all, excessive periods of time are required for the compositions to harden or set. The compositions also have a tendency to shrink as much as percent by volume thereby rendering difiicult the production of large numbers of refractory elements possessing uniform dimensions. In addition, the resulting cast refractory articles often possess poor mechanical strength.

The use of special techniques, such as pressure or vacuum-casting has been proposed as a possible means for obviating these difficulties. ever, require considerable amounts of equipment and their use therefore is often only justified where large numbers of refractory articles are to be produced. Another drawback to these special techniques is that, in general, only castings possessing relatively simple physical configurations can be produced from fibrous refractory materials; these techniques not being suitable for the production of refractory articles possessing substantially irregular shapes.

According to the present invention, I have found that these aforementioned difficulties can be largely eliminated by the use of casting compositions containing certain fibrous refractory materials and a hydration-type binder compound.

I have also discovered that improved castable compositions are obtained by adding the hydration binder compound to compositions containing the fibrous refractory materials and a non-hydration type binder compound.

It is therefore an object of the invention to provide novel fibrous refractory compositions which are capable of being cast into a variety of physical configurations using simple techniques.

A further object is to provide cast refractory articles of a variety of physical shapes possessing good chemical and thermal characteristics.

Another object is to provide a simple and effective method for producing these shaped refractory articles.

Other objects of the invention and the advantages thereof will become apparent hereinafter.

In general, the hydration binders used in conjunction with the fibrous refractory materials, according to the present invention, are those which are capable of imparting the required mechanical strength to cast refractory elements as well as both transforming the water present in the casting composition into hydrate form and retaining this water of hydration at the temperatures to which the final casting is expected to be exposed.

These techniques, how- 3,253,936 Patented May 31, 1966 More particularly, the hydration binder compounds which are used in the castable compositions of the present invention are selected from calcium aluminate (CaA1 O or CaO.Al O and certain hydraulic cements known as high-alumina or calcium aluminate cements, containing predominant proportions (more than 50%) of calcium aluminate. The term calcium aluminate distinguishes these cements from other cement materials such as Portland cement wherein calcium silicates are the principal constituents.

These hydration-type binders act by reacting with the water present in the casting mixture to form hydration products, thus insuring that the major portion of this water is retained upon the setting of the casting. The hydration binders therefore effect the setting of the casting by means of a hydration mechanism as distinguished from an evaporation mechanism.

The use of calcium aluminate or calcium aluminate cements as the hydration binder is critical. Thus the employment of other binder materials, including those which function by a hydration mechanism such as Portland cement, does not result in the superior castable compositions of this invention.

The particular amount of hydration binder employed will depend on the particular nature of the other materials present in the casting composition. The hydration binder must be employed in an amount sufficient to form hydration products with predominant amounts of the water present in the castable composition. In general, from about 2 to about 60%, preferably from about 10 to 40%, based on the weight casting composition, is used.

The particular refractory materials employed in the casting compositions of this invention are alumina-silica fibers containing from about 5-95 alumina and from about 595% silica, or potassium titanate fibers. Refractory materials of this'type may be present in a very finely divided state so long as they possess the fiber structure.

In general, these refractory fibers possess a weight in the range from about 10 to about 120 lbs. per cubic ft. of material. Alumina-silica fibers in the range from about 70 to about lbs. per cubic ft., and potassium titanate fibers in the range from about 30 to about 40 lbs. per cubic ft. are preferred.

Particularly good results are obtained when milled alumina-silica fibers of the type supplied under the name Fiberfrax are employed. Fibrous materials of this type are light weight, inert to most acids and retain their I desirable properties at temperatures as high as 3000" F. Potassium titanate fibers of the type supplied under the name Tipersul are also suitable for use.

The refractory fibers may be used in amounts from about 20 to about 90%, preferably from about 40 to about 80%, based on the weight of the castable composition.

According to a preferred aspect of the present invention, it has been found that the addition of the aforementioned hydration binder materials to castable compositions containing either alumina-silica fibers or potassium titanate fibers as well as a non-hydration binder material, results in castable compositions which are capable of being formed, in an advantageous manner, into shaped articles possessing particularly superior mechanical and thermal characteristics.

The non-hydration binders are materials which either, because of their chemical composition or particular physical form (e.g., water dispersions or aqueous solutions), cause the setting of the castable composition to proceed by an evaporation mechanism.

Suitable non-hydration binder materials include aqueous solutions or colloidal dispersions of Groups I or II metal aluminates or metal silicates in water and aqueous colloidal dispersions or suspensions of silica. The amounts of water present as the solvent or dispersing phase in these non-hydration binder materials can, of

simple casting techniques. able composition in the form of a flowable mass at room temperature may be poured into a suitable mold. The casting is allowed a sufiicient time to set and the mold is course, vary widely depending on the particular ma- 5 then removed. Of course, other and more complicated terial. The. only requirement is that at least enough casting techniques using elevated temperatures, controlled water be used to form the' solution or dispersion. Colpressure, etc., may be employed, but it is a particular loidal suspensions or dispersions of silica containing from advantage of the castable compositions of the present inabout 45 to 85% Water are particularly preferred.v vention that the use of such techniques is not necessary The proportions of the non-hydration binder will dein order to produce refractory castings possessing good pend on the nature and amount of the other components mechanical characteristics even at temperatures of the of the composition. order of 20003000 F. or higher.

Generally, the amount of the non-hydration binder ma- The following specific embodiments are given in order terial used varies from about 2 toabout 40% of the to further illustrate the present invention. Unless othercastable composition. wise indicated all parts and proportions are by weight.

The amount of water present in the entire castable EXAMPLE 1 composition may also vary considerably. It is preferred to employ water in suflicient amounts so as to form a TWenty eashhg eomposlhohs eohtalhlng the followlngi Substantiany free-flowing mix having appearance of 19 gm. (40.8%) of alumina-silica fibers, supplied under conventional concrete mixes. In general, the total water 20 h name Fiberfrax 100, content Inely vmy from. about 5 to about 40% of the 17 gm. (36.6%) calcium aluminate (approximately 99% weight of the composition. d

The Water y be added e to the other e 10.5 gm. (22.6%) of a suspension of colloidal silica in p h ei when hbh'hydrahoh blhders are used, elther water containing about 35% silica and supplied under a port o 012: 0r 4 entlfe he Of Water y be the name Rigidizer (water comprises about 14% of tamed 1n th sbindencomposition and added to the castthe total casting composition), were prepared and east able eomposltlon 1h to form refractory elements suitable for use as burner 1 The casttlzliblfe 1iompositlons of1 thlis intvention surprisingair Cones in gun type oil burners ossess e o owing IlIlCl a a van ages: 1) Only a very sn iall. a inount of shrinkage occurs CASTING PROCEDURE during the setting of the castings. The casting composi- The burner air bones were cast in 2 3 Piece Silicon tions shrink during setting generally no more than Thbher molds- Except for the Pouring and Vent holes, about the molds were closed. The required amount of refrac- (2) A i ifi t decrease in the time necessary f r tory material was mixed with water and/or binder, formthe casting to set is obtained. For'example, fibrous casth a flowa'ble material having a consistehey pp ing compositions which lack a hydration-type binder 111g Common concrete The at room temperature, may require several days to set, whereas a similar casting Poured through meld Pouring hole into the moldcomposition containing the hydration hinder requires a Entrained air bubbles were removed through the vent holes Setting time f only a few hours. with the aid of vibration. The use of vibration is optional (3) Conventional simple casting techniques using 40 and depends P mold complexity desired casting either open or Closed molds can he used There is he finish. The refractory casting was allowed sufficient time need to resort to pressure injection and vacuum techniques to Set and the mold was then removed- The Small amount Whieh often require considerable apparatue of free Water, which was not used in the hydration reaction (4) The castings produced from the instant fibrous e which remained in the Casting, was Temoved y "yrefractory compositions containing hydrate binders posmg at sess mechanical characteristics significantly superior to Examples eesthlgs P p from Compositions lacking Ihis yp of Four casting mixes were prepared. Three of these blndermixes contained calcium aluminate as the hydration bind- The a e compos'ltw-ns of the Present lnventlon y er, while the remaining mix contained no hydration binder further contain effective amounts of other ingredients materiah normally used in eOmPOSIfiOHS Of this yp Such as P Each of the mixes was then cast in a l-piece test mold e, accelerators, wofkeblllty agents, (1.465 inches long and .735 inch in diameter). The set fol'mlhg agents, h time, the linear shrinkage, and the casting density (gm./

Refractory castings of any desired shape and s1ze may cc.) were determined for each mix. The results are rebe prepared from the mstant compositions by employing ported in the following table.

TABLE E NIgple Casting Mix Composition (R ob in h e ii p) sh r h i li ge, Percent gmjcc.

Etta; ilitttiiifiitfiifitiif hm 48 9.1 8 62.5% (25 g.) milled alumina-silica fibers 12.5% (5 g.) calcium aluminate cement" }3 hours 3. 2 1. 76 25% (10 g.) silica suspension 4 50% (20 g.) milled alumina-silica fibers 25% (10 g.) catcium aluminate cement }2 hours 2. 4 1. 25% (10 g.) 110a suspension 232% }2 hours 1. 1 1. 78

1 Aluminas ilica fibers supplied under the name Fiberfrax 2 A suspension of colloldal silica in water containing about 35% by weight of silica and supplied under the name Rigidizer.

3 The water present in the silica suspension com rises a roximatel 16 of h approximately 14% of the mix in Example 5. p pp y t 6 mm m Examples and Thus, for example, the cast- It will be seen from the results reported in the table that the castable compositions of Examples 3-5, which contained the hydration binder, set in 3 hours or less, and exhibited a linear shrinkage of no more than 3.2%. By contrast, the castable composition of Example 2 required 48 hours to set and exhibited a linear shrinkage of 9.1%.

While certain representative embodiments and details have been set forth for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therefrom without departing from the spirit and scope of the present invention.

Having thus fully described the invention, what I desire to secure and claim by Letters Patent is:

1. A castable composition suitable for producing refractory articles consisting essentially of (1) from about 20% to about 90% by weight of total composition of a fibrous refractory material selected from the group consisting of alumina-silica fibers and potassium titanate fibers;

(2) from about 2% to about 60% by weight of total composition of calcium aluminate hydration binder;

(3) from about 2% to about 40% by weight of total composition of silica in the form of an aqueous colloidal dispersion containing from about 15 to about 55 by weight of silica; and

(4) the remainder of said composition being Water in sufiicient quantity to form hydration products with said calcium aluminate hydration binder material.

2. The composition of claim 1 in which the said fiber is alumina-silica fiber.

3. A castable composition suitable for producing refractory articles consisting essentially of 1) from about 40% to about 80% by weight of total composition of alumina silica fibers;

2) from about to about 40% by weight of calcium aluminate;

' 6 (3) from about 2% to about 40% by weight of silica in the form of an aqueous colloidal dispersion containing from about to about 55% by Weight of silica and 5 (4) the remainder of said composition being water in suflicient quantity to form hydration products with said calcium aluminate hydration binder. 4. A process for preparing shaped refractory articles which comprises the steps of (A) forming a composition containing (1) from about to about 90% by Weight of a fibrous refractory material selected from the group consisting of alumina-silica fibers and potassium titanate fibers, (2) from about 2% to about 60% by weight of calcium aluminate hydration binder, (3) from about 2% to about by weight of a mixture of water and silica in the form of an aqueous colloidal dispersion containing from about 15 to about by weight of silica, and (4) Water in sufficient quantity to form hydration products with said calcium aluminate and to render said composition a fiowable mass, (B) pouring said composition into a mold, (C) closing said mold and allowing said composition to set, while removing any air bubbles from said mold-enclosed composition, and (D) separating said mold from the set composition and removing any residual water therefrom. 5. The process of claim 4 wherein the amount of calcium aluminate is from about 10% to about 40% by 30 weight.

References Cited by the Examiner UNITED STATES PATENTS 2,793,128 5/1957 Emhiser 106104 5 2,917,426 12/1959 Bugosh 10639 3,100,734 8/1963 Rex 106--65 TOBIAS E. LEVOW, Primary Examiner. 

1. A CASTABLE COMPOSITION SUITABLE FOR PRODUCING REFRACTORY ARTICLES CONSISTING ESSENTIALLY OF (1) FROM ABOUT 20% TO ABOUT 90% BY WEIGHT OF TOTAL COMPOSITION OF A FIBROUS REFRACTORY MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALUMINA-SILICA FIBERS AND POTASSIUM TITANATE FIBERS; (2) FROM ABOUT 2% TO ABOUT 60% BY WEIGHT OF TOTAL COMPOSITION OF CALCIUM ALUMINATE HYDRATION BINDER; (3) FROM ABOUT 2% TO ABOUT 40% BY WEIGHT OF TOTAL COMPOSITION OF SILICA IN THE FORM OF AN AQUEOUS COLLOIDAL DISPERSION CONTAINING FROM ABOUT 15% TO ABOUT 55% BY WEIGHT OF SILICA; AND (4) THE REMAINDER OF SAID COMPOSITION BEING WATER IN SUFFICIENT QUANTITY TO FROM HYDRATION PRODUCTS WITH SAID CALCIUM ALUMINATE HYDRATION BINDER MATERIAL. 